Composition and method for controlling insect, mite and nematode pests with s-(n-alkoxyamido)-thiophosphoramides



United States Patent 3,403,208 COMPOSITION AND METHOD FOR CON- TROLLINGINSECT, MITE AND NEMA- TODE PESTS WITH S-(N-ALKOXYAMIDO)-THIOPHOSPHORAMIDES Sidney B. Richter, Chicago, Ill., assiguor toVelsicol Chemical Corporation, Chicago, 11]., a corporation of DelawareNo Drawing. Original application Aug. 4, 1964, Ser. No. 387,491, nowPatent No. 3,342,905, dated Sept. 19, 1967. Divided and this applicationJuly 21, 1967, Ser. No. 654,959

2 Claims. (Cl. 424-211) ABSTRACT OF THE DISCLOSURE An insecticidal,miticidal and nematocidal composition comprising an inert carrier and,in a quantity toxic to insects, mites and nematodes a compound of theformula H O /OR RPS-R4- -N R2N-R3 R0 wherein R R R R and R areindependently selected from the group consisting of hydrogen and alkyl;and R is an alkylene group.

This application is a division of my copending application Ser. No.387,491 filed Aug. 4, 1964, now U.S. Patent No. 3,342,905 issued Sept.19, 1967.

This invention relates to new chemical compositions of matter. Morespecifically, this invention relates to new chemical compounds of theformula wherein R R R R and R are independently selected from the groupconsisting of hydrogen and alkyl groups containing from one to tencarbon atoms; and R is selected from the group consisting of alkylenegroups containing from one to ten carbon atoms. In a preferredembodiment of this invention, the above mentioned alkyl and alkylenegroups each contain from one to four carbon atoms. These new chemicalcompounds are useful as pesticides, particularly as insecticides,miticides, and nematocides.

The new compounds of this invention can be prepared readily from thecorresponding alkali metal salts of the O-alkyl-amido-thiolphosphoricacid intermediates. These intermediates having the formula wherein R Rand R are as described above are reacted with the corresponding knownN-alkoxy-N-alkyl-haloalkylamides of the formula Cl-R --C(O)N(OR (Rwherein R R and R are as described above to form the desired compoundsof the present invention. In a preferred embodiment of this invention anexcess of the alkali metal salt is used and in a most preferredembodiment about a ten percent excess of the salt concentration over theamide concentration is employed.

The alkali metal salts of the O-alkyl-amido-thiolphosphoric acid can beprepared by a two-step synthesis. The starting material is thecorresponding dialkyl halothionophosphate of the formula (R O) P=(S)(Cl) wherein R is as described above. It is treated with a suitableamine of the formula HN(R (R or amine hydrochloride of the formula HN(R)(R )-HCI wherein R and R are as described above. When the free amine isemployed, an amount about double the molar concentration of the startingmaterial should be used. When the amine is used Patented Sept. 24, 1968in the form of its hydrochloride, an amount at least about equimolarwith the starting material should be employed, with the preferred molarconcentration of the amine hydrochloride being slightly greater than themolar concentration of the starting material. Also, when the aminehydrochloride is used, an acid scavenger such as a tertiary amine shouldbe employed in an amount about double the molar concentration of theamine hydrochloride present. The resulting product is then treated withalkali such as potassium hydroxide, sodium hydroxide and the like in amolar ratio of about one part of the product of step one to about onepart alkali, to yield the alkali metal salt ofO-alkyl-amido-thionophosphoric acid, having the formula R OP(S) (NR R)(ONa) wherein R R and R are as described above. These salts are capableof reacting through rearrangement, in the form of the desired alkalimetal salts of the O-alkyl amidothiolphosphoric acids.

Suitable dialkyl halothionophosphate starting materials are known to theart. Examples thereof are dimethylthionochloridate,dimethylthionobromidate, diethylthionochloridate,diethylthionobromidate, di-n-propylthionochloridate,diisopropylthionochloridate, di-n-butylthionochloridate,di-sec-butylthionochloridate, ditert-butylthionochloridate,dipentylthionochloridate, dihexylthionochloridate,diheptylthionochloridate, dioctylthionochloridate,dinonylthionochloridate, didecylthionochloridate,

and the like.

Exemplary amines suitable for the treatment of the aforementionedphosphates are also known to the art, some of them are methylamine,dimethylamine, ethylamine, diethylamine, n-propylamine,di-n-propylamine, isopropylamine, diisopropylamine, n-butylamine,secbutylamine, tert-butylamine, di-n-butylamine, di-sec-butylamine,di-tert-butylamine, pentylamine, dipentylamine, hexylarnine,dihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine,nonylamine, dinonylamine, decylamine, didecyl-amine and the like.

Suitable N-alkoxy-N-alkylhaloalkyl amides which can be reacted with themetal salts of the O-alkyl amidothiolphosphoric acids to give thedesired product of the present invention are N-methoxy-N-methyla-chloroacetamide, N-ethoxy-N-ethyl a-chloroacetamide, N-methoxy-N-ethyla-chloroacetamide, N-ethoxy-N-methyl a-chloroacetamide,N-methoxy-N-n-propyl a-chloroacetamide, N-methoxy-N-isopropyla-chloroacetamide, N-n-propoxy-N-propyl a-chloroacetamide,N-isopropoxy-N-isopropyl u-chloroacetamide, N-butoxy-N-butyla-chloroacetamide, N-pentoxy-N-pentyl a-chloroacetamide,N-hexoxy-N-hexyl a-chloro'acetamide, N-heptoxy-N-heptyla-chloroacetamide, N-octoxy-N-octyl u-chloroacetarnide, N-nonoxy-N-nonylu-chloroacetamide, N-decoxy-N-decyl u-chloroacetamide,N-methoxy-N-methyl a-chloropropionamide, N-ethoxy-N-ethyla-chloropropionamide, N-methoxy-N-n-propyl u-chloropropionamide,N-n-propoxy-N-methyl a-chloropropionamide, N-methoxy-N-isopropyla-chloropropionamide,

and the like.

The manner in which new compounds of this invention can be prepared isillustrated in the following examples:

EXAMPLE 1 Preparation of 0,0-diethyl-N,N-dimethylthionophosphorarnidateDiethylthionophosphochloridate (40 g., 0.21 mole), dimethylaminehydrochloride (17 g., 0.21 mole) and triethylamine (42 g.) in benzene(100 ml.) were placed into a 250 ml. flask and refluxed with stirringfor 17 hours. The reaction mixture was cooled to room temperature andfiltered. The filter cake was washed with benzene and the washings werecombined with the filtrate. This combined solution was evaporated underreduced pressure on a steam bath and the residue was vacuum distilled toyield 0,0 diethyl N,N dimethylthionophosphoramidate.

EXAMPLE 2 o OCH:

cnno-ii-s-om-iLr/ OHg-N-OHs CH3 0,0diethyl-N,N-dimethylthionophosphoramidate (8 g.; 0.041 mole) was treatedwith 85% pure potassium hydroxide (2.8 g.; .043 mole) dissolved inabsolute ethanol (50 ml.) in a 250 ml. flask. The reaction mixture wasrefluxed for 17 hours with stirring. The excess solvent was removedunder reduced pressure with heating and the residue was allowed to coolto room temperature and then washed two times with ether. This residuewas then treated with N-methoxy-N-methyl a-chloroacetamide (4.1 g.; .03mole) dissloved in absolute ethanol 50 ml.). The reaction mixture wasrefluxed with stirring for 17 hours in a 250 ml. flask and then cooledto room temperature and filtered. The filter cake was washed withethanol and the washings were combined with the filtrate. This combinedsolution was evaporated under reduced pressure on a steam bath. Theresidue from this evaporation was dissolved in chloroform, washed withwater and dried over magnesium sulfate. The solution was then filteredand evaporated under reduced pressure on a steam bath. Evaporation wascontinued for an additional hour under a vacuum pressure of 0.1 mm. Hgto yield O-ethyl- S[N'-methoxy-N'-methylacetamido]-N,N-dirnethylthiophosphoramide.

Analysis for C H N O PS.Theory, percent: N, 10.73. Found, percent: N,10.06.

EXAMPLE 3 Preparation of 0,0-diethyl-N-isopropylthionophosphoramidateEXAMPLE 4 o CH3 oinso-i -s-ong-iLN rmomorn): omen:

0,0 diethyl-N-isopropylthionophosphoramidate (31.7 g.; 0.15 mole) wastreated with 85% pure potassium hydroxide (10 g.; 0.15 mole) dissolvedin absolute ethanol (250 ml.) in a 500 ml. flask. This reaction mixturewas refluxed for 17 hours with stirring. The excess solvent was removedunder reduced pressure with heating and the residue was allowed to coolto room temperature and then washed thoroughly with ether. A portion ofthis residue (9.0 g.; .04 mole) was treated with N- methoxy N isopropyla chloroacetamide (50 g.; .03 mole) and benzene ml.) in a 300 ml. roundbottomed flask. The mixture was stirred and heated to reflux and allowedto reflux with stirring overnight. The reaction .mixture was cooled andthen filtered. The benzene was [removed from the filtrate by aspiration.The residual oil was dissolved in ether and the ether solution waswashed twice with water. The ether was then dried over anhydrous{magnesium sulfate. The magnesium sulfate was filtered off and the etherwas removed by aspiration leaving a yellow oil. This oil was subjectedto aspiration by means of a vacuum pump and was allowed to be soaspirated overnight. The oil was then filtered through super cel(suction filtration). This product was again filtered yielding 0ethyl-S-[N'-methoxy-N'-isopropylacetamido]-N-isopropylthiophosphorarnide.

Analysis for C N N O PS.Theory, percent: S, 10.25; P, 9.93. Found,percent: S, 10.94; P. 9.73.

OCH3

Dimethylthionophosphochloridate (32 g.; 0.20 mole) and dimethylaminehydrochloride (9.4 g.; 0.21 mole) are reacted according to the procedureof Example 1. The product obtained is treated with potassium hydroxide(11.2 g.; 0.20 mole) and N-methoxy-N-methyl a-chloroacetamide (18 g.;0.15 mole) according to the procedure of Example 2, to obtainO-methyl-S-[N-methoxy-N- methylacetamido] -N,N-dimethylthiophosphoramide.

Di-n-propylthionophosphochloridate (43.2 g.; 0.20 mole) andisopropylamine hydrochloride (12.2 g.; 0.21 mole) are reacted accordingto the procedure of Example 1. The product obtained is treated withpotassium hydroxide (11.2 g.; 0.20 mole) and N-methoxy-N-rnethyla-chloroacetamide (18 g.; 0.15 mole) according to' the procedure ofExample 2, to obtain O-n-propyl-S-[N'- methoxy-N'-methylacetamido] Nisopropylthiophos- OCHs phoramide.

EXAMPLE 8 O O C Ha (CHs)2CHO-i. S-CHz( /-N HNCH(CH3)2 CH3Diisopropylthionophosphochloridate (43.0 g.; 0.20

EXAMPLE 9 Dimethylthionophosphochloridate (37.4 g.; 0.20 mole) andisopropylamine hydrochloride (9.5 g.; 0.21 mole) are reacted accordingto the procedure of Example 1. The product obtained is treated withpotassium hydroxide (11.2 g.; 0.20 mole) and N-methoxy-N-isopropylachloroacetamide (24.8 g.; 0.15 mole) according to the procedure ofExample 2 to obtain O-methyl-S-(N- methoxy-N-isopropylacetamido)N-isopropylthiophosphoramide.

EXAMPLE 10 O OCHs Diethylthionophosphochloridate (37.4 g.; 0.20 mole)and ethylamine hydrochloride (9.5 g.; 0.21 mole) are reacted accordingto the procedure of Example 1. The product obtained is treated withpotassium hydroxide (11.2 g.; 0.20 mole) and N-methoxy-N-methyla-chloroacetamide (18 g.; 0.15 mole) according to the procedure ofExample 2 to obtain O-ethyl-S-(N-methoxy-N'- methylacetamido-N-ethylthiophosphoramide.

EXAMPLE 1 1 OCH;;

Diethylthionophosphochloridate (37.4 g.; 0.20 mole) and n-propylaminehydrochloride (12.4 g.; 0.21 mole) are reacted according to theprocedure of Example 1. The product obtained is treated with potassiumhydroxide (11.2 g.; 0.20 mole) .and N-methoxy-N-methyl a-chloroacetamide(18 g.; 0.15 mole) according to the procedure of Example 2 to obtainO-ethyl-S-(N-methoxy-N'- methylacetamido)-N-n-propylthiophosphoramide.

EXAMPLE 12 I (I) /OCH3 C2H50IS-CH2(N HNC4H9 CH3Diethylthionophosphochloridate (37.4 g.; 0.20 mole) and n-butylaminehydrochloride (15.3 g.; 0.21 mole) are reacted according to theprocedure of Example 1. The product obtained is treated with potassiumhydroxide (11.2 g.; 0.20 mole) and N-methoxy-N-methyl a-chloroacetarnide(18 g.; 0.15 mole) according to the procedure of Example 2 to obtainO-ethyl-S-(N'-methoxy-N'- methylacetamido) -N-n-butylthiophosphoramide.

Diethylthionophosphochloridate (37.4 g.; 0.20 mole) and sec-butylaminehydrochloride (15.3 g.; 0.21 mo1e) are reacted according to theprocedure of Example 1. The product obtained is treated with potassiumhydroxide (11.2 g.; 0.20 mole) and N-methoxy-N-methyl uchloroacetamide(18 g.; 0.15 mole) according to the procedure of Example 2 to obtainO-ethyl-S-(N-methoxy- N-methylacetamido) -N-sec-butylthiophosphoramide.

HNC (CH9: CH3

Diethylthionophosphochloridate (27.4 g.; 0.20 mole) and tert-'butylaminehydrochloride (15.3 g.; 0.21 mole) are reacted according to theprocedure of Example 1. The product obtained is treated with potassiumhydroxide (11.2 g.; 0.20 mole) and N-methoxy-N-methyl a-chloroacetamide(18 g.; 0.15 mole) according to the procedure of Example 2 to obtainO-ethyl-S-(NFmethoxy-N-methylacetamido-N-tert-butylthiophosphoramide.

Diethylthionophosphochloridate (37.4 g.; 0.20 mole) and isopropylaminehydrochloride (12.4 g.; 0.21 mole) are reacted according to theprocedure of Example 1. The product obtained is treated with potassiumhydroxide (11.2 g.; 0.20 mole) and N-methoxy-N-methyl achloroa-methylacetamide (22.6 g.; 0.15 mole) according to the procedure ofExample 2 to obtain O-ethyl-S- (N' methoxy N methyl a-methylacetamido)-N-is0 propylthiophosphoramide.

-Diethy1thionophosphochloridate (37 .4 g.; 0.20 mole) and isopropylaminehydrochloride (12.4 g.; 0.21 mole) are reacted according to theprocedure of Example 1. The product obtained is treated with potassiumhydroxide (11.2 g.; 0.20 mole) and N-ethoxy-N-ethyl a-chloroacetamideOCH3 r (24.6 g.; 0.15 mole) according to the procedure of Ex- Di nbutylthionophosphochloridate+isopropylamine +potassiumhydroxide+N-methoxy N methyl oc-ClllO- roacetamide=0 nbutyl-S-(N-meth0xy-N'-methylacetamido) -N-isopropylthiopho sphoramide.

EXAMPLE 18 Di sec-butylthionophosphochloridate+isopropylamine +potassiumhydroxide+N-methoxy-N-methy1 a-ChlOlO- acetamide=O-sec butylS-(N'-meth0xy-N'-methylacetamido) -N-isopropylthiophosphoramide.

EXAMPLE 19 Di tert butylthionophosphochloridate'+isopropylamine+potassium hydroxide+N-methoxy-N-methyl occhloroacetamide=0tert-butyl-S-(N'-rnethoxy-N'-methylacetamido)-N-isopropylthiophosphoramide.

EXAMPLE 20 Diethylthionophosphochloridate-I-di n propylamine +potassiumhydroxide+N-methoxy-N-methyl a-chloroacetamide=0 ethyl S(N'-methoxy-N'-methylacetamido)-N,N-di-n-propylthiophosphoramide.

EXAMPLE 21 Diethylthionophosphochloridate diisopropylamine potassiumhydroxide-l-N methoxy- N-methyl zx-ChlOIO- 7 acetamide= ethyl S(N-methoxy-N-methylacetamido) -N,N-diisopropylthiophosphoramide.

EXAMPLE 22 Diethylthionophosphochloridate isopropylamine potassiumhydroxide+N-methoxy N methyl Ct-ChlOI'O- n-butyramide=0 ethyl S(N'-methoxy-N'-methyl-nb utyramido -N-isopropylthiophosphoramide.

EXAMPLE 23 Diethylthionophosphochloridate isopropylamine potassiumhydroxide-|-N ethoxy N methyl a chloroacetamide=0 ethyl S (N ethoxyN'-methylacetamido) N isopropylthiophosphoramide.

EXAMPLE 24 Diethylthionophosphochloridate+isopropylamine+potassiumhydroxide-i-N n propoxy-N-n-propyl OL-ChlOI'O- acetamide=0 ethyl S (Nn-propoxy-N-n-propylacetamido)-N-isopropylthiophosphoramide.

EXAMPLE 25 Diethylthionophosphochloridate+isopropylamine+potassiumhydroxide-i-N isopropoxy N isopropyl occhloroacetamide=0 ethyl S (Nisopropoxy N isopropylacetamide)-N-isopropylthiophosphoramide.

For practical use as insecticides, miticides and nematocides thecompounds of this invention are generally incorporated intoinsecticidal, miticidal and nematocidal compositions which comprise aninert carrier and an insecticidally, miticidally or nematocidally toxicamount of such a compound. Such compositions, which are usually known inthe art as formulations, enable the active compound to be appliedconveniently to the site of the insect, mite or nematode infestation inany desired quantity. These compositions can be solids such as dusts,granules, or Wettable powders, or they can be liquids such as solutionsor emulsifiable concentrates.

For example, dusts can be prepared by grinding and blending the activecompound with a solid inert carrier such as the tales, clays, silicas,pyrophyllite, and the like. Granular formulations can be prepared byimpregnating the compound, usually dissolved in a suitable solvent, onto and into granulated carriers such as the attapulgites or thevermiculites, usually of a particle size range of from about 0.3 to 1.5mm. Wettable powders, which can be dispersed in water to any desiredconcentration of the active compound, can be prepared by incorporatingwetting agents into concentrated dust compositions.

In some cases the active compounds are sufficiently soluble in commonorganic solvents such as kerosene or xylene so that they can be useddirectly as solutions in these solvents. Frequently, solutions ofinsecticides, miticides or nematocides can be dispersed undersuperatmospheric pressure as aerosols. However, preferred liquid rEXAMPLE 27 Preparation of a dust Product of Example 2 10 Powdered talc90 The above ingredients are mixed in a mechanical grinder-blender andare ground until a homogeneous, freeflowing dust of the desired particlesize is obtained. This dust is suitable for direct application to thesite of the insect, mite or nematode infestation.

The insecticides, miticides and nematocides of this invention can beapplied in any manner recognized by the art. The concentration of thenew compounds of this invention in the insecticidal, miticidal ornematocidal compositions will vary greatly with the type of formulationand the purpose for which it is designed, but generally the compositionswill comprise from about 0.05 to about percent by weight of the activecompounds of this invention. In a preferred embodiment of thisinvention, the compositions will comprise from about 5 to about 75percent by weight of the active compound. The compositions can alsocomprise such additional substances as other pesticides, spreaders,adhesives, stickers, fertilizers, activators, synergists, and the like.

The new compounds of this invention can be used in many ways for thecontrol of insects. Insecticides which are to be used as stomach poisonsor protective materials can be applied to the surface on which theinsects feed or travel. Insecticides which are to be used as contactpoisons or eradicants can be applied directly to the body of the insect,as a residual treatment to the surface on which the insect may walk orcrawl, or as a fumigant treatment of the air which the insect breathes.In some cases, the compounds applied to the soil or plant surfaces aretaken up by the plant, and the insects are poisoned systemically.

The above methods of using insecticides are based on the fact thatalmost all the injury done by insects is a direct or indirect result oftheir attempts to secure food. Indeed, the large number of destructiveinsects can be classified broadly on the basis of their feeding habits.There are, for example, the chewing insects such as the Mexican beanbeetle, the southern armyworm, cabbageworms, grasshoppers, the Coloradopotato beetle, the cankerworm, and the gypsy worm. There are also thepiercing-sucking insects, such as the pea aphid, the house fly, thechinch bug, leafhoppers, and plant bugs.

Another group of insects comprises the internal feeders. These includeborers such as the European corn borer and the corn earworm; worms orweevils such as the codling moth, cotton boll weevil, plum curculio,melonworm, and the apple maggot; leaf miners such as the apple leafminer and the beet leaf miner; and gall insects such as the wheatjointworm and grape phylloxera. Insects which attack below the surfaceof the ground are classified as subterranean insects and include suchdestructive pests as the wooly apple aphid, the Japanese beetle, and thecorn rootworm.

Mites and ticks are not true insects. Many economically importantspecies of mites and ticks are known, including the red spider mite, thestrawberry spider mite, the cattle tick, and the poultry mite. Chemicalsuseful for the control of mites are often called rniticides, while thoseuseful for the control of both mites and ticks are known specifically asacaricides.

The quantity of active compound of this invention to be used for insectcontrol will depend on a variety of factors, such as the specific insectinvolved, intensity of the infestation, weather, type of environment,type of formulation, and the like. For example, the application of onlyone or two ounces of active chemical per acre may be adequate forcontrol of a light infestation of an insect under conditions unfavorablefor its feeding, while a pound or more of active compound per acre maybe required for the control of a heavy infestation of insects underconditions favorable to their development.

When the compounds of this invention are used as nematocides to controlor prevent infestations of destructive nematodes, they are ordinarilyused as soil treatments. Plant parasitic nematodes occur in enormousnumbers in all kinds of soil in which plants can grow, and many plantpathologists believe that all the crop and ornamental plants grown inthe world can be attacked by these nematodes. The destructive species ofnematodes range from the highly specialized, which attack only a fewkinds of plants, to the polyphagous, which attack a great many differentplan-ts. The plants almost invariably become infected by nematodes thatmove into them from the soil. The underground parts of plants, roots,tubers, corns, and rhizomes are thus more apt to be infected thanabove-ground parts, but infection of stems, leaves, and flower parts isalso fairly common.

Damage to plants attacked by nematodes is due pri marily to the feedingof the nematodes on the plant tis sues. The nematodes may enter theplant to feed, may feed from the outside, or be only partially embedded.The feeding of a nematode may kill the cell or may simply interfere withits normal functioning. If the cell is killed, it is often quicklyinvaded by bacteria or fungi. If the cell is not killed, it and theadjacent cells may be stimulated to enlarge or multiply. Hence the mostcommon types of nematode damage are manifested as rotting of theattacked parts and adjacent tissue or the development of galls and otherabnormal growths. Either can interfere with the orderly development ofthe plant and cause shortening of stems or roots, twisting, crinkling ordeath of parts of stems and leaves, and other abnormalities.Consequently, the yield of crop plants is reduced, while a high-qualitycrop cannot be produced from the crippled plants.

The use of the compounds of this invention for nematode control can makethe difference between a good crop and one not worth harvesting. Oncethe nematodes are controlled, yield increases of 25 to 50 percent arenot uncommon. The solid or liquid nematocidal compositions of thisinvention can be applied to the soil, or in some cases to the plants andsoil, in any convenient manner. While broadcast applications to the soilbefore planting by conventional plow or disc methods are effective,specialized methods such as row placement application, splitdosageapplications, post-planting sidedress applications, and the like arealso useful. The active compounds of this invention are applied inamounts sufiicient to exert the desired nematocidal action. The amountof the active compound present in the nematocidal compositions asactually applied for preventing or controlling nematode infestationsvaries with the type of application, the particular species which are tobe controlled, and the purpose for which the treatment is made, and thelike.

The utility of the compounds of the present invention was illustrated,for example, by experiments carried out for the control of insects. Thetest compound was formulated by dissolving the compound in acetone anddispersing the acetone solution in distilled water containing 0.2% byvolume of alkyl aryl polyether alcohol type emulsifier.

In one experiment fifty adult houseflies of the CSMA strain were placedin a 2-inch by 5-inch diameter stainless steel cage having screening (14mesh) at its top and bottom. The flies were sprayed with the aboveformulation containing the amount of test compound indicated below, andthe mortality was observed 2 hours and 24 hours after spraying. Theresults were as follows:

TABLE I Concn., percent Percent mortality Test chemical actual chem.(wt/vol. 2 hrs. 24 hrs.

liquid sprayed)O-ethyl-S-(N-methoxy-N-methylacetamido)-N,N-dimethylthiophosphoramide0.35 98 100 O-ethyl-S- (N -methoxyl-N -isopropylacetamido)-N-isopropylthiophosphoramide 0. 1- 100 100 0.35 100 100 0.0 0 0 The utility of thecompounds of this invention was further illustrated by additionalexperiments carried out for the control of insects, by feeding. In theseexperiments, lima bean leaves sprayed on their top and bottom surfaceswith the above formulation at the concentrations indicated below wereoffered to ten larvae of the Mexican bean beetle (late second instarstage) for a feeding period of 48 hours. After this period mortality wasobserved. The results were as follows:

In still another test, the utility of the compounds of this invention asan insecticide was further illustrated by spraying adult pea aphids withthe above formulation containing the indicated amount of test compound,transferring the aphids to pea plants also sprayed with the formulation,and observing the mortality after 48 hours. The results were as follows:

TABLE III Concn., percent actual Test chemical chem Percent (wt/volmortality liquid sprayed)O-ethyl-S-(N-methoxy-N-methylacetamido)-N,N-dimethylthiophosphoramide 0.35 O-ethyl-S-(N'-methoxy-N-isopropylacetamido)-N-isopropylthiophosphoramide. 0. 1 100 Do 0. 35 100 Control. 0. 0 0

The utility of the compounds of the present invention as miticides wasillustrated in experiments for the control of strawberry spider mites(Tetranychus atlanticus). In these experiments lima bean plantspreviously infested with from 50 to 100 adults of the mites were dippedinto the formulations and held for five days. Thereafter, the adultmortality rate was observed, The results were as follows:

TABLE IV Concn., percent actual Test chemieal chem. Percent (wt./volmortality liquid sprayed)O-ethyl-S-(N-methoxy-N-metl1ylacetamido)-N,N-dimethylthiophosphoramide0. 35 100 O-ethyl-S-(N-methoxy-N '-is0propylacetamido)-N-isopropylthiophosphoramide. 0. 1 100 Do 0. 35 100 Control 0. 0 0

The compounds of the present invention also have utility as nematocides.This utility was illustrated in experiments for the control'ofMeloidogyne spp. nematodes. In one experimental procedure, the testchemicals formulated as in the above insecticidal tests atconcentrations indicated below were poured on mixtures of soil alreadyinfested with nematodes, greenhouse sterilized soil and sand mixed in aratio of one part infected soil to three parts sterile soil to 1 partsand until this test soil Wa drenched. After storage of the soil forseven days in open plastic pots with daily watering, tomato plants weretransplanted into this soil as a host for the nematodes. Nematodecontrol by the test chemicals was evaluated three to six weekssubsequent to the transplanting by comparison of the degree of gallingof the tomato plants in treated and untreated soil. In this experiment,O-ethyl-S-(N- methoxy-N'-isopropylacetamido) Nisopropylthiophosphoramide gave the following results:

TABLE V Concn., actual chem. Percent control Phytotoxicity l (lbs/4 inchacre) d Ehytotoxicity based on 0-10 index. 0 indicates no damage and 10Contr0l18.5 galls/plant.

The utility of the compounds of the present invention as nematocides wasfurther illustrated employing another experimental procedure. In thisexperiment, the test chemicals were formulated as described above atconcentrations indicated below. The soil mixtures were also the same asabove (i.e. one part infected soil to 3 parts sterile soil to 1 partsand). The test chemical was added to the soil and the soil and chemicalwere mixed by shaking and kneading the soil in a polyethylene bag. Thebag of treated soil was then placed in a l-pint widemouth mason jar,tightly sealed, and the jars were stored for seven days at a constanttemperature of 76 F. After the seven day storage, the soil wastransferred from the bag to clean plastic pots on a greenhouse bench andthe soil was kept moist for an additional seven days. Next, a tomatoplant was transplanted into the pot and allowed to grow for three to sixweeks, after which time the soil was washed from the tomato roots andthe galls on the roots were counted. The degree of nematode control bythe test chemicals was evaluated by comparison of the degree of gallingof tomato plants in treated and untreated soil. In this experi- 12 ment,O-ethyl-S- (N '-methoxy-N '-iso pro pylacetamido -N-isopropylthiophosphoramide gave the following results:

TABLE VI Concn., actual chem. Percent control Ihytotoxicity 1 (lbs/4inch acre) d 1 ghytotoxicity based on 0-10 index. 0 indicates no damageand 10 Control12 galls/plant.

I claim:

1. An insecticidal, miticidal and nematocidal composition comprising aninert carrier and, in a quantity toxic to inserts, mites and nematodes acompound of the formula 1 R10P-SR4J)N R2NRa R0 wherein R R R R and R areindependently selected from the group consisting of hydrogen and alkyl;and R is an alkylene group.

2. A method for controlling insert, mite, and nematode pests whichcomprises applying to said pests an insecticidal, miticidal andnematocidal composition comprising an inert carrier and as the essentialactive ingredient, in a quantity which is toxic to said pests, acompound of claim 1.

References Cited FOREIGN PATENTS 923,702 4/1963 Great Britain.

ALBERT T. MEYERS, Primary Examiner.

S. J. FRIEDMAN, Assistant Examiner.

